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Production and Application ofCellulose Nanomaterials
Michael Bilodeau
Director, Process Development Center
University of Maine
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Outline
• UMaine Process Development Center
• Introduction to Cellulose Nanomaterials
• Partnerships
• Applications
• Commercialization Activities
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UMaine Process Development Center
• Department of Chemical and Biological Engineering
• Not-for-Profit Contract Research Group
• Self Supporting
• Professional Staff
• Fee-for-Service Basis
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Serving the Needs of Industry Since 1987
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Innovation Continuum – R,D,& C Its Cyclical – not Linear
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Valley of Death
Basic Research
Applied Research
Production/Public Access
DevelopmentDemonstration Commercialization
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Univ and Non-profit R&D Commercial R&D
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Business & Markets Drive
Science & Technology Drives
$ Fed Grants –NIH,NSF, etc.
$ Fed GrantsDoD ,DOE ,USDA.
$$ -Regional & State Seed Grants, Development Awards, Fed SBIR
$$ VC --Equity-- Debt
$ Company Funds – Family, Fools and Friends
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Operating Model
• Partner with Industry
• Collaborate with other Institutions & Agencies
• Coordinate Project Activities
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Academia
PrivatePublic
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Pilot Capabilities
• Pilot paper machine
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• Web coater / laminator
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Example of Private-Public Partnership
High Speed Pilot Coater - Client Owned and Operated
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Example of Private-Public Partnership
Specialty Paper Machine - Client Owned and Operated
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Introduction to Cellulose Nanomaterials
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Cellulose based nanoparticles
Cellulose Based MaterialsCellulose Derivatives
Functionalize -OH
• Cellulose Acetate• Hydroxyethyl Cellulose• Methyl cellulose• Carboxymethyl Cellulose
Fiber
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Lumber
Microcrystalline Cellulose
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Courtesy Dr. Robert Moon USFS
http://en.wikipedia.org/wiki/File:Toothpasteonbrush.jpghttp://en.wikipedia.org/wiki/File:Toothpasteonbrush.jpghttp://4.bp.blogspot.com/-upi6rmFpi6I/UT2v7_UGkXI/AAAAAAAAMtc/yEE9iFyuTBk/s1600/ice-cream-cone-soap-set.jpghttp://4.bp.blogspot.com/-upi6rmFpi6I/UT2v7_UGkXI/AAAAAAAAMtc/yEE9iFyuTBk/s1600/ice-cream-cone-soap-set.jpghttp://blog.bostonsight.org/wp-content/uploads/2013/05/eyedrops1.jpghttp://blog.bostonsight.org/wp-content/uploads/2013/05/eyedrops1.jpg
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Cellulose Nanofibrils
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What are Cellulose Nanomaterials (CNs)?
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• Nano-sized particles isolated from:• trees, plants, algae
• Highly ordered cellulose chains: • parallel stacking of chains• ordered & disordered domains
“Nano Effect”:• Fewer defects• Aligned chains
Properties:• Length• Aspect ratio• Crystallinity
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Courtesy Dr. Robert Moon USFS
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Dufresne et al., J. App. Poly. Sci., 1997
Cellulose Nanofibrils (CNF)
Cellulose Nanocrystals (CNC)
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Several “Flavors” of CNs
Acid HydrolysisAll
Biomass
Chem/Mech
Mechanical
Particles:• Source• Method
Properties:• Length• Aspect Ratio• Branching• Crystallinity
Rod-like•D=3-20 nm•L=50-500 nm•Low branching
Fibril-like:•D=3-40 nm•L=100s nm - >1µm•Branching
May 19, 2015 E2 Tech Meeting - BioBased Maine
Courtesy Dr. Robert Moon USFS
http://4.bp.blogspot.com/-upi6rmFpi6I/UT2v7_UGkXI/AAAAAAAAMtc/yEE9iFyuTBk/s1600/ice-cream-cone-soap-set.jpghttp://4.bp.blogspot.com/-upi6rmFpi6I/UT2v7_UGkXI/AAAAAAAAMtc/yEE9iFyuTBk/s1600/ice-cream-cone-soap-set.jpg
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Cellulose Nanofibrils
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• Fibril width 10 – 100 nm• Lengths up to 10’s of microns• High aspect ratio (100 – 1000)• Large specific surface area
(100-200 g/m2 )
x 100k 200 nm
SEM image of isolated
Cellulose Nanofibrils
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History of Nanocellulose
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Reduced to practice by ITT Rayonier, 1977Patented in 1983 – Turbak, et. al.
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CNF Related Patents
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CNF Related Publications
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Why CNF Again?
• Three Major Driving Forces– Breakthrough lower cost manufacturing methods
– New, novel application technology
– National priorities driving federal funding
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Scalable
Low Energy
Low Capital
Applications
Overcoming Commercial Barriers
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Partnerships
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US Forest Service#1 Priority – Forest Fire Suppression
•>$1 MM/hr spent fighting forest fires
•More than ½ of USFS annual Budget
•Millions of acres need “Restoration”
•Only 200,000 acres/yr restored.
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UMaine CNF Pilot Facility
• Capability– Refiner CNF
• Pre-treatment
– Mass Colloider Grinder
• Capacity– 1 ton/day
– Slurry form (3% solids)
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UMaine CNF Pilot Facility
• Availability– Fee-for-service basis
– Samples available
• Kg to tonne quantities
• CNF & CNC
• Slurry or dry
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UMaine CNF Pilot Facility
• Spray Dryer – Several kg/day capacity
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Cellulose Nanomaterials Distributed
between April 2013 – February 2015
• Samples provided to – 167 private companies
– 119 academic institutions
– 25 research centers
– In 35 different countries
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Applications
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Rheology Modifier• Paints• Cosmetics• Food• Adhesives
Separators/Barrier• Filtration• Batteries• Pumps• …
Commercial Application Areas
Specialty Packaging
Herrera et al.
Vartiainen et al.
Flexible Electronics• Self Powered• Display• Solar• LED• … Yano et al.
Tissue Engineering
• Scaffolds• Bandages• Ligament• Blood Vessels• Drug Delivery
Deng et al.
Continuous Fibers
Dong et al., 2012
• Reinforcement• Textiles• Woven• …
Specialty Cements
Cao et al.
• Foamed• Panel• Siding• …
Foams
Paakko et al., Soft Matter, 2008
• Acoustic• Structural• Thermal• …
Production• Yields• Process• Costs
May 19, 2015 E2 Tech Meeting - BioBased MaineCourtesy Dr. Robert Moon USFS
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Commercial Scale-upRelease Base Paper Surface
Control – 208 X CN 200 – 245 X
5% CNF added
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Stain ResultsSilicone Coated Release Base
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A. Control Base B. CN 200 Base
Pilot paper machine samples 5% CNF
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Paper Coated with CNF
X 500
X 500
X 500
0.5 g/m2 coating
1.5 g/m2 coating
3.0 g/m2 coating
20 µm 20 µm
20 µmMay 19, 2015
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Ink density of Ink Jet Printed Samples
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CNF improves ink jet print quality
EKA Chemicals Inc.
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Polymer Composites
Neat Silicone 1% L-CNC 2% L-CNC
1% CNC in PLA
Agglomerates
1% TEMPO CNF in PLA
Conventional Bleached CNC & CNFVery poor dispersion
Neat PE 1% L-CNC in PE
Neat PHB 1% L-CNC in PHB
BioPlus L-CNCVery uniform dispersion
Neat PS 1% L-CNC in PS0.3% L-CNC in PLA
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BioPlus Compostable Bags● Strong ● Renewable ● Compostable ● PLA + BioPlus L-CNC
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Vehicle Light Weighting Project• Objective: Development of a sprayable binder resin
system containing nanocellulose as a reinforcing phase to replace steel in seating assemblies– Opportunity to achieve commercial application on
electric vehicles
• Results: Clark ATL has successfully dispersed L-CNC in the hydrophobic resin system of choice
• Impact: Reducing a vehicle’s weight by just 10 percent can improve fuel economy by 6-8 percent
– U.S. DOE’s target vehicle weight reduction is 50% by 2050.
– According to the DOE the limiting factor in use of lightweight materials in vehicles is availability of sufficient quantities at affordable cost1
ReinforcingMaterial Density (g/cm3)
Calcium carbonate 2.71
Talc 2.69
E-glass fiber 2.5
Carbon fiber 1.8
Nanocellulose 1.5
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3D Printing Project
• Objective: Reinforce 3D printing feedstock with high temperature stability, highly dispersableBioPlus-L™ to obtain desired mechanical properties for load-bearing parts
• Impact: Replace high cost, peutroleum–based carbon fiber as reinforcing agent for high temperature polymers like ABS, PLA, Nylon 6,6, and PC with renewable, biobased nanocellulose.
• Phase II Goal: Print a golf cart from nanocellulose reinforced polymer using Oak Ridge’s Big Area Manufacturing (BAAM) facility.
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CNF Films
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Industrial Epoxy Coatings
40Link
Link
Link
Link
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http://www.symet.com/Content/files/industrialBeamBlasting.jpghttp://www.symet.com/Content/files/industrialBeamBlasting.jpghttp://www.csscorp.net/cc/wp-content/uploads/2011/04/Anti-Corr-AFTER.jpghttp://i00.i.aliimg.com/photo/v0/105422798/industrial_flooring_cement.jpghttp://www.symet.com/Content/files/WisconsinPumpCoatingEpoxy.JPGhttp://www.symet.com/Content/files/WisconsinPumpCoatingEpoxy.JPG
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Commercialization Activities
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Ref: Shatkins, JTappi Nano ConferenceVancouver, BC 2014.
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Commercial Start-ups
• American Process Inc. – Thomaston, GA
– BioPlus “Pre-commercial” plant - 0.5 tpd capacity
– CNF and CNC capacity
– Started-up April 2015
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API’s Thomaston Biorefinery
Fractionation and Cellulose Separation
Biomass
Was
he
d
cellu
lose
Regenerated Solvent, SO
2
Liquor (hemicelluloses solvent, SO
2, lignin)
Enzymatic Hydrolysis
Glucose to
chemicals conversion Hemicelluloses Sugars to Ethanol / Butanol
Lignin to energy and chemical applications
Hemicelluloses Auto Hydrolysis
Chemical Regeneration
Cellulose products
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BioPlus Demonstration Line
Screening & Cleaning
Mechanical Treatment
Product Cooling & Storage
Bleach Plant
½ ton per dayStart-up in April 2015
Located at Thomaston Biorefinery
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Commercial Start-ups
• Paperlogic Paper – Turners Falls, MA
– Commercial CNF plant - 2 tpd capacity
– Internal and merchant sales
– Started-up May 14, 2015
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Contacts
Michael Bilodeau, Director
Email: [email protected]
Phone: 207-581-2387
Pros Bennett, Managing Director
Email: [email protected]
Phone: 207-949-4176
www.umaine.edu/pdc
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mailto:[email protected]:[email protected]